WO2012061464A1 - Arsenic-free spinel glass-ceramics with high visible transmission - Google Patents

Arsenic-free spinel glass-ceramics with high visible transmission Download PDF

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Publication number
WO2012061464A1
WO2012061464A1 PCT/US2011/058903 US2011058903W WO2012061464A1 WO 2012061464 A1 WO2012061464 A1 WO 2012061464A1 US 2011058903 W US2011058903 W US 2011058903W WO 2012061464 A1 WO2012061464 A1 WO 2012061464A1
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Prior art keywords
glass
composition
ceramic material
ceramic
material according
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PCT/US2011/058903
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French (fr)
Inventor
Etienne Almoric
Marie Jacqueline Monique Comte
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Corning Incorporated
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Priority to JP2013537777A priority Critical patent/JP6049141B2/en
Priority to CN201180062746.XA priority patent/CN103298760B/en
Priority to KR1020137014308A priority patent/KR101951963B1/en
Publication of WO2012061464A1 publication Critical patent/WO2012061464A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods

Definitions

  • the present disclosure relates to transparent glass-ceramic materials which contain a spinel solid solution as the main crystalline phase, corresponding precursor alumino-silicate glasses, articles made of said transparent glass-ceramic materials as well as a method for manufacturing such articles, and structures comprising a sheet made of such glass-ceramic materials and electronic or optoelectronic devices comprising such structures.
  • the transparent spinel glass-ceramics display a high transmission in the 400-1000 nm range and are environmentally friendly (free of arsenic and antimony). They are industrially obtained in an easy way insofar as their precursor alumino-silicate glasses show suitable liquidus (low temperature of liquidus and high viscosity at this temperature).
  • Some transparent spinel glass-ceramics also display interesting strain points and coefficient of thermal expansion. They are suitable substrates for high temperature growth of high quality monocrystalline or poly crystalline silicon thin films for example. Structures including such substrates with such thin films thereon can be used in photovoltaic devices, flat panel devices and liquid crystal devices.
  • US Patent No. 4,687,750 relates to transparent glass-ceramics containing gahnite.
  • the composition of the precursor glasses contains Ti0 2 as nucleating agent. Minor amounts of Zr0 2 may be included in the composition without adversely affecting the properties of the crystallized products. Nonetheless it is explained that Zr0 2 is unnecessary as a nucleating agent as Ti0 2 is a much more efficient nucleating agent. Moreover Zr0 2 is much less soluble than Ti0 2 in the glass, hence its presence hazards unmelted particles and/or devitrification in the glass and requires higher melting temperature.
  • a fining agent such as AS2O3 and/or Sb 2 03 may be added to the batch.
  • US Patent No. 5,476,821 describes high modulus glass-ceramics containing fine grained spinel-type crystals. Nucleation efficiency is enhanced by the presence of components such as Ti0 2 , Zr0 2 and NiO, and also high levels of A1 2 0 3 .
  • US Patent No. 5,968,857 describes transparent glass-ceramics containing spinel as a predominant crystal phase.
  • the composition of the precursor glasses contains Ti0 2 and/or Zr0 2 as nucleating agents. Fining agents such as As 2 C"3 or Sb 2 C"3 may be added to said precursor glass compositions.
  • L.R. Pinckney the inventor of said US Patent No. 5,968,857, has also disclosed such transparent spinel glass-ceramics which display high strain point in the Journal of Non-Crystalline Solids, 255 (1999), pp. 171-177.
  • the described glass-ceramics are able to withstand thermal treatments at 1000°C without deformation.
  • L.R. Pinckney has observed that precursor glasses melted with Ti0 2 (but without arsenic) leads to glass-ceramics showing a gray color and so having a low transmission in all the visible range.
  • US Patent Application No. 2005/0096208 describes glass-ceramics containing spinel, sapphirine or cordierite as a main crystalline phase. Said glass- ceramics can be obtained in forming precursor glasses by the float method and then by ceramming the formed glasses.
  • B 2 O 3 is an essential component of the composition of the precursor glasses.
  • P 2 O 5 , Ti0 2 , Zr0 2 , Sn0 2 and Ta 2 0 5 are proposed as nucleating agents.
  • Sn0 2 is also proposed as fining agent.
  • WO Patent Application 2007/144875 also describes glass-ceramics containing spinel as a main crystalline phase.
  • Ti0 2 is disclosed as a preferred nucleating agent. It may be used in a large amount.
  • the Figure shows complete transmission curves (as a function of wavelength) of comparative examples A and B and inventive examples 1 and 3.
  • the inventors have considered the technical problem of providing spinel glass-ceramics (i) free of any toxic fining agent (free of AS 2 O 3 and Sb 2 0 3 ), (ii) showing a high transmission in the visible and near IR (such a high transmission is very important in the case of photovoltaic or equivalent applications: the glass-ceramic used as superstrate so allows a maximum of solar energy to reach the silicon layer), i.e.
  • the transparent spinel glass-ceramics disclosed herein also display a high strain point (higher than 850°C, more preferably higher than 875°C and most preferably higher than 900°C), as well as a CTE in the 30-40x10 " 7 K _1 range (25-300°C).
  • a high strain point higher than 850°C, more preferably higher than 875°C and most preferably higher than 900°C
  • CTE in the 30-40x10 " 7 K _1 range 25-300°C.
  • Said advantageous characteristics are particularly advantageous if the glass-ceramics are aimed to be used as substrates for layer(s) made of a semi-conductor, especially for crystalline silicon layer(s). Therefore, their CTE provides a relatively close thermal match to silicon, and their high strain point allows to be used them as a substrate to make high quality crystalline silicon by growth at high temperature (> 850°C).
  • glass-ceramics disclosed herein have more particularly been developed in reference to the five above stipulations (so as to be particularly suitable as substrate for layer(s) made of a semi-conductor, especially for crystalline silicon layer(s)) but that the disclosure also encompasses glass-ceramics complying with only the first three stipulations and usable in others contexts. Such transparent spinel glass-ceramics are easily obtained, free of toxic fining agent and are per se interesting.
  • Tin oxide is known as a possible substitute to arsenic for fining in alumino-silicate glasses.
  • tin oxide in the composition of glass-ceramics, said glass-ceramics obtained from a precursor glass with a suitable liquidus and said glass-ceramics having a high transmission.
  • the removal of arsenic leads to a strong absorption in the visible range and the removal of titanium oxide and its replacement by zirconium oxide leads to transparent material but with an inacceptable liquidus (> 1500°C).
  • titanium containing glass-ceramics tend to have a strong absorption in the 400-450 nm range, probably due to the existence of a charge transfer between titanium and iron brought as an impurity by the raw materials. This absorption is enhanced when tin oxide is added.
  • a transparent glass-ceramic material free of As and Sb and containing a spinel solid solution as the main crystalline phase.
  • the composition of said material (expressed in percentages in weight) is free of As 2 0 3 and Sb 2 0 3 , with the exception of unavoidable trace thereof, and comprises Sn0 2 , Ti0 2 and Zr0 2 , and less than 100 ppm of Fe 2 0 3 .
  • a transparent material here means a material showing a transmission of at least 50% for any wavelength in the 400-450 nm range (preferably higher than 70% for any wavelength in the 400-450 nm range), higher than 80% for any wavelength in the 450-520 nm range and higher than 85% for any wavelength in the 520-1000 nm range, such a transmission being measured through a thickness of 1 mm of material.
  • the main crystalline phase observed in the material is a spinel solid solution of formula (Zn,Mg)Al 2 0 4 (being it not impossible that other elements like titanium or iron enter in the solid solution). It represents at least 75% (in weight %) of the crystalline matter.
  • Other crystalline phases present within the material of the invention could be for example srilankite or quartz.
  • the mean size of the spinel crystalites is typically lower than 10 nm.
  • the composition of the material includes Sn0 2 as fining agent, both Ti0 2 and Zr0 2 as nucleating agents, and less than 100 ppm of Fe 2 0 3 , to generate a spinel glass-ceramic with a high transmission.
  • Sn0 2 is efficient as fining agent. It seems also to play a role as nucleating agent and help to limit the level of titanium oxide. It is advantageously present at the indicated level of 0.1 - 2 wt. %, and it is very advantageously present at the indicated level of 15 - 0.8 wt. %. The fining efficiency and the absorption both increase with the tin oxide level.
  • Ti0 2 is advantageously present (very advantageously present) within the indicated ranges. It has to be efficient enough as nucleating agent (otherwise the material is not transparent) and not responsible of a strong absorption.
  • Zr0 2 is advantageously present within the indicated range. It has to be efficient enough as nucleating agent and not responsible of devitrification.
  • the disclosed glasses display liquidus temperature lower than 1500°C and a viscosity at the liquidus higher than 700 dPa.s
  • Iron is an impurity which may be introduced by the raw materials. Iron can be present at a concentration of less than 100 ppm to limit absorption. Its level is advantageously less than 80 ppm, very advantageously it is less than 60 ppm.
  • the glass-ceramic materials have a composition, expressed in percentage by weight of oxide, which essentially consists of:
  • the composition "essentially consists of the given list of compounds (oxides). This means that in the glass-ceramic materials according, the sum of the listed compounds (oxides) represents at least 95 weight %, generally at least 98 weight %. It cannot be excluded that other compounds may be found in low quantities in said glass-ceramic materials (obviously any other compounds that have not a strong detrimental action on the required properties, more particularly on transparency). So the presence of Ce0 2 is (quasi) excluded (the composition of the glass-ceramics generally includes no Ce0 2 ), also the significant presence of B 2 0 3 (the composition of the glass-ceramics generally includes no B 2 0 3 ).
  • the composition advantageously comprise more than 55 % by weight of Si0 2 and within said composition, the molar ratio (R 2 0 + R0)/A1 2 03 is between 0.5 to 1.5, R 2 0 being the sum of the moles of alkali oxides and RO the sum of the moles of alkaline earth oxides plus ZnO.
  • Glass-ceramics with such composition have a high strain point, of generally at least 875°C (at least 900°C).
  • A1 2 0 3 is one of the main component of the crystals. It can be present at a minimum amount to ensure sufficient crystallization and not at a too high amount to then produce an unacceptable devitrification of mullite, hence the above indicated preferred range.
  • ZnO and MgO are also constituents of the crystals. Therefore a minimum amount can be incorporated. At a too high level, MgO is detrimental for transparency. The above indicated preferred values take that into account.
  • BaO stays in the residual glass. It has been observed that it helps in having a good transparency but its amount has to be limited to keep enough crystallinity and a high strain point, hence the above indicated preferred range.
  • the precursor glass as well as the glass-ceramics are environmentally free (are arsenic and antimony free).
  • the precursor glass is easily formed.
  • the glass-ceramics are transparent and display a high transmission above 400 nm which, combined with a high strain point, more particularly makes them suitable as superstrate for photovoltaic cells.
  • Some of the glass-ceramics are more particularly suitable to support the high temperature growth of a mono crystalline or poly crystalline semiconductor layer.
  • Such growth may consist in the epitaxial thickening of a seed layer formed on the glass-ceramic material.
  • the seed layer may be a large grain polycrystalline silicon layer formed by Aluminum Induced Crystallization or Aluminum Induced Layer Exchange (O. Nast, T. Puzzer, L.M. Koschier, A.B. Sproul, S.R. Wenham, Appl. Phys. Lett. 73 (1998) 3214), or may be a monocrystalline silicon layer (WO 2008/121262).
  • the epitaxial thickening of such layers is advantageously performed at temperatures above 800 °C, and more advantageously performed at temperatures above 1000°C (I. Gordon et al, Solar Energy Materials & Solar Cells 94 (2010) 381-385).
  • Another means of achieving a high quality polycrystalline silicon layer is to perform a high temperature rapid thermal annealing step of a previously grown polycrystalline silicon layer (B. Rau et al, Materials Science and Engineering B 159-160 (2009) 329-332).
  • Photovoltaic cells usually include at least one transparent conductive layer located between the superstrate and the at least one semiconductor absorber layer.
  • a transparent conductive layer allows the collection of the charge carriers generated in the semiconductor absorber layer, while allowing most of the photons to reach the semiconductor absorber layer.
  • the transparent conductive layer may be a transparent conductive oxide layer, or more advantageously, in the case of an epitaxial thickening of a seed layer, may be the seed layer itself in the event that it is a highly doped layer.
  • the transparent conductive layer usually has significant absorption below a wavelength of 400 nm, which does not result in the generation of collectable charge carriers. Therefore a superstrate should preferably have a high transmission for wavelengths above 400 nm.
  • this semi-transparent conductive layer usually has significant absorption up to a wavelength of about 450 nm.
  • a superstrate should preferably have a high transmission for wavelengths above 450 nm. In this way the glass-ceramics of the invention are particularly suitable as superstates for photovoltaic cells.
  • the present disclosure relates to alumino-silicate glass materials which are precursor of the glass-ceramic materials described above.
  • Such glass materials advantageously have the compositions indicated above (for the glass-ceramics).
  • the level of zirconium oxide can be kept at a low enough level to limit devitrification.
  • the co- presence of Ti0 2 and Zr0 2 allows the requirements to be satisfied.
  • the present invention also relates to articles made of glass-ceramic materials described above.
  • Such glass-ceramic articles may present any shape and may be aimed to any use.
  • they consist in a sheet.
  • Such sheets generally have a thickness in the range of 0.5 to 4 mm.
  • Such sheets are advantageously used as support (substrate) for semiconductor thin films.
  • the present disclosure relates to a method for manufacturing an article made of a glass-ceramic material as described above.
  • Said method successively includes melting of a batch mixture of raw materials able to vitrify, said batch mixture containing Sn0 2 as refining agent, followed by refining of the molten glass obtained, cooling of the refined molten glass obtained, and simultaneously forming it into a desired form for the targeted article, and ceramming of said formed glass, said batch mixture being a precursor of a glass-ceramic material as described above.
  • Said method is characteristically carried out with a suitable mineral batch mixture (including Sn0 2 as fining agent, Ti0 2 and Zr0 2 as nucleating agents and less than 100 ppm of Fe 2 0 3 , advantageously in the amounts as more precisely described above) and with a suitable heat-treatment which provides a spinel glass-ceramic.
  • a suitable mineral batch mixture including Sn0 2 as fining agent, Ti0 2 and Zr0 2 as nucleating agents and less than 100 ppm of Fe 2 0 3 , advantageously in the amounts as more precisely described above
  • the ceramming treatment generally comprises the two steps: a nucleation step (in the 700-850°C range) and a step of crystal growth (in the 850 -
  • the forming step of said method is advantageously carried out to produce a sheet.
  • it very advantageously consists in rolling (between rollers) or in a float process.
  • the produced sheet generally has a thickness of 0.5 to 4 mm.
  • Any sheet produced by the above method is opportunely a part of a structure including, further to said sheet, at least one layer made of a semi-conductor (arranged on said sheet).
  • a structure constitutes a further subject-matter.
  • the disclosure relates to electronic and optoelectronic devices comprising such a structure (glass-ceramic sheet + at least one layer made of a semi-conductor).
  • Such devices may consist in a photovoltaic device, a flat panel display device, a liquid crystal display device. Said list is in no way exhaustive.
  • the raw materials in proportions (weight proportions expressed as oxides) copied out in the first part of Table 1 hereafter, have been mixed carefully for producing batches of 1 kg of precursor glass. It has to be noted that said raw materials includes impurities (as traces), more particularly traces of Fe 2 C"3.
  • the transmission measurements have been performed on 1 mm thick polished samples with a spectrophotometer equipped with an integrating sphere (this allows to measure the total, i.e. direct + diffuse, transmission).
  • the lines "T 80%", “T 85%” and “T 90%” (of the second part Table 1 hereafter) give the wavelengths (in nm) at which the transmission values of 80%>, 85% and 90% are respectively reached. The lower values are better.
  • the temperature is decreased to the test temperature, at 10°C/min; maintenance at the test temperature for 17h;
  • Examples A, B, C and D do not belong to the invention. They are comparative examples.
  • the glass of comparative example A contains AS 2 O 3 . It is a glass according to US Patent No. 5,968,857.
  • the glass of comparative example B has quasi the same composition as the one of the glass of comparative example A. However, its composition is free of AS 2 O 3 . As explained above, it displays a low transmission.
  • the glass of comparative example C does not contain arsenic but a lower titanium level than the glass of comparative example B. Its transmission is higher but still low.
  • the glass of comparative example D contains a lower level of iron than the one of comparative example C. It displays a higher transmission but still much lower than the one of comparative example A (with AS 2 O 3 ).
  • Examples 1-6 are inventive.
  • Example 1 is preferred.
  • example B is low and that transmission of examples A, 1 and 3 is higher than 80% for any wavelength above 450nm and higher than 85% for any wavelength higher than 520 nm. It also shows that the transmission of example 1 is especially interesting with a transmission higher than 80% for any wavelength higher than 400 nm.

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Abstract

A transparent glass-ceramic materials contains a spinel solid solution as the main crystalline phase and is free of As2O3 and Sb2O3. Corresponding precursor alumino-silicate glasses, articles made of said transparent glass-ceramic materials as well as a method for manufacturing such articles, and structures comprising a sheet made of such glass-ceramic materials and electronic or optoelectronic devices comprising such structures are also disclosed. Some materials disclosed can be used as substrates for high temperature growth of high quality monocrystalline or polycrystalline silicon thin films. Structures including such substrates with such thin films thereon can be used in photovoltaic devices, flat panel devices and liquid crystal devices.

Description

ARSENIC-FREE SPINEL GLASS-CERAMICS
WITH HIGH VISIBLE TRANSMISSION
CROSS-REFERENCE TO RELATED APPLICATION(S)
[0001] This application claims the benefit of priority under 35 U.S.C. § 119 of European Patent Application Serial No. 10306207.1 filed on November 4, 2010, the content of which is relied upon and incorporated herein by reference in its entirety.
STATEMENT REGARDING SPONSORED RESEARCH
[0002] This invention was funded in part by a grant from "Agence Nationale de la Recherche" under grant ANR-07-PSPV-004-05 for the POLYSIVERRE project under the program "Solaire Photo volta'ique."
BACKGROUND
[0003] The present disclosure relates to transparent glass-ceramic materials which contain a spinel solid solution as the main crystalline phase, corresponding precursor alumino-silicate glasses, articles made of said transparent glass-ceramic materials as well as a method for manufacturing such articles, and structures comprising a sheet made of such glass-ceramic materials and electronic or optoelectronic devices comprising such structures.
[0004] The transparent spinel glass-ceramics display a high transmission in the 400-1000 nm range and are environmentally friendly (free of arsenic and antimony). They are industrially obtained in an easy way insofar as their precursor alumino-silicate glasses show suitable liquidus (low temperature of liquidus and high viscosity at this temperature).
[0005] Some transparent spinel glass-ceramics also display interesting strain points and coefficient of thermal expansion. They are suitable substrates for high temperature growth of high quality monocrystalline or poly crystalline silicon thin films for example. Structures including such substrates with such thin films thereon can be used in photovoltaic devices, flat panel devices and liquid crystal devices.
[0006] Spinel glass-ceramics have been disclosed in numerous prior art documents. [0007] US Patent No. 3,681,102 discloses transparent glass-ceramic articles comprising zinc spinel. The composition of the precursor glasses contains Zr02 as a nucleating agent and, conventionally, a fining agent such as AS2O3 may be included in the batch materials.
[0008] US Patent No. 4,687,750 relates to transparent glass-ceramics containing gahnite. The composition of the precursor glasses contains Ti02 as nucleating agent. Minor amounts of Zr02 may be included in the composition without adversely affecting the properties of the crystallized products. Nonetheless it is explained that Zr02 is unnecessary as a nucleating agent as Ti02 is a much more efficient nucleating agent. Moreover Zr02 is much less soluble than Ti02 in the glass, hence its presence hazards unmelted particles and/or devitrification in the glass and requires higher melting temperature. To improve glass quality, a fining agent such as AS2O3 and/or Sb203 may be added to the batch.
[0009] US Patent No. 5,476,821 describes high modulus glass-ceramics containing fine grained spinel-type crystals. Nucleation efficiency is enhanced by the presence of components such as Ti02, Zr02 and NiO, and also high levels of A1203.
[0010] US Patent No. 5,968,857 describes transparent glass-ceramics containing spinel as a predominant crystal phase. The composition of the precursor glasses contains Ti02 and/or Zr02 as nucleating agents. Fining agents such as As2C"3 or Sb2C"3 may be added to said precursor glass compositions.
[0011] L.R. Pinckney, the inventor of said US Patent No. 5,968,857, has also disclosed such transparent spinel glass-ceramics which display high strain point in the Journal of Non-Crystalline Solids, 255 (1999), pp. 171-177. The described glass-ceramics are able to withstand thermal treatments at 1000°C without deformation. L.R. Pinckney has observed that precursor glasses melted with Ti02 (but without arsenic) leads to glass-ceramics showing a gray color and so having a low transmission in all the visible range. Such a low transmission is an impediment to the use of these glass-ceramics in photovoltaic applications and the like as it reduces the amount of light which is able to reach the silicon. L.R. Pinckney suggests that a partial reduction of titanium in Ti3+ is responsible for the very strong absorption in the visible. Actually, it appears that, in addition to its fining effect, arsenic also plays a role of bleaching agent.
[0012] US Patent Application No. 2005/0096208 describes glass-ceramics containing spinel, sapphirine or cordierite as a main crystalline phase. Said glass- ceramics can be obtained in forming precursor glasses by the float method and then by ceramming the formed glasses. B2O3 is an essential component of the composition of the precursor glasses. P2O5, Ti02, Zr02, Sn02 and Ta205 are proposed as nucleating agents. Sn02 is also proposed as fining agent.
[0013] WO Patent Application 2007/144875 also describes glass-ceramics containing spinel as a main crystalline phase. Ti02 is disclosed as a preferred nucleating agent. It may be used in a large amount.
BRIEF DESCRIPTION OF THE DRAWING
[0014] The Figure shows complete transmission curves (as a function of wavelength) of comparative examples A and B and inventive examples 1 and 3.
DETAILED DESCRIPTION
[0015] In such a context, the inventors have considered the technical problem of providing spinel glass-ceramics (i) free of any toxic fining agent (free of AS2O3 and Sb203), (ii) showing a high transmission in the visible and near IR (such a high transmission is very important in the case of photovoltaic or equivalent applications: the glass-ceramic used as superstrate so allows a maximum of solar energy to reach the silicon layer), i.e. showing (under a thickness of 1 mm) a transmission of at least 50% for any wavelength in the 400-450 nm range (preferably higher than 70% for any wavelength in the 400-450 nm range), higher than 80% for any wavelength in the 450-520 nm range and higher than 85% for any wavelength in the 520-1000 nm range, and (iii) for which the precursor glasses display a liquidus lower than 1500°C and a viscosity at the liquidus higher than 700 dPa.s. This is obviously in reference to an easy forming of said precursor glasses.
[0015] Advantageously, the transparent spinel glass-ceramics disclosed herein also display a high strain point (higher than 850°C, more preferably higher than 875°C and most preferably higher than 900°C), as well as a CTE in the 30-40x10" 7K_1 range (25-300°C). Said advantageous characteristics are particularly advantageous if the glass-ceramics are aimed to be used as substrates for layer(s) made of a semi-conductor, especially for crystalline silicon layer(s). Therefore, their CTE provides a relatively close thermal match to silicon, and their high strain point allows to be used them as a substrate to make high quality crystalline silicon by growth at high temperature (> 850°C).
[0016] We incidentally note here that the glass-ceramics disclosed herein have more particularly been developed in reference to the five above stipulations (so as to be particularly suitable as substrate for layer(s) made of a semi-conductor, especially for crystalline silicon layer(s)) but that the disclosure also encompasses glass-ceramics complying with only the first three stipulations and usable in others contexts. Such transparent spinel glass-ceramics are easily obtained, free of toxic fining agent and are per se interesting.
[0017] Tin oxide is known as a possible substitute to arsenic for fining in alumino-silicate glasses. However, it was not at all obvious to have tin oxide in the composition of glass-ceramics, said glass-ceramics obtained from a precursor glass with a suitable liquidus and said glass-ceramics having a high transmission. As explained above, the removal of arsenic leads to a strong absorption in the visible range and the removal of titanium oxide and its replacement by zirconium oxide leads to transparent material but with an inacceptable liquidus (> 1500°C). Moreover, titanium containing glass-ceramics tend to have a strong absorption in the 400-450 nm range, probably due to the existence of a charge transfer between titanium and iron brought as an impurity by the raw materials. This absorption is enhanced when tin oxide is added.
[0018] The inventors have actually surprisingly discovered that the co- presence of Ti02 and Zr02 as nucleating agents together with a low level of iron allow the use of Sn02 as substitute for As203 in the obtaining of suitable transparent spinel glass-ceramics.
[0019] Therefore, disclosed herein is a transparent glass-ceramic material, free of As and Sb and containing a spinel solid solution as the main crystalline phase. Characteristically the composition of said material (expressed in percentages in weight) is free of As203 and Sb203, with the exception of unavoidable trace thereof, and comprises Sn02, Ti02 and Zr02, and less than 100 ppm of Fe203. [0020] A transparent material here means a material showing a transmission of at least 50% for any wavelength in the 400-450 nm range (preferably higher than 70% for any wavelength in the 400-450 nm range), higher than 80% for any wavelength in the 450-520 nm range and higher than 85% for any wavelength in the 520-1000 nm range, such a transmission being measured through a thickness of 1 mm of material.
[0021] The main crystalline phase observed in the material is a spinel solid solution of formula (Zn,Mg)Al204 (being it not impossible that other elements like titanium or iron enter in the solid solution). It represents at least 75% (in weight %) of the crystalline matter. Other crystalline phases present within the material of the invention could be for example srilankite or quartz. The mean size of the spinel crystalites is typically lower than 10 nm.
[0022] Characteristically, the composition of the material includes Sn02 as fining agent, both Ti02 and Zr02 as nucleating agents, and less than 100 ppm of Fe203, to generate a spinel glass-ceramic with a high transmission.
[0023] Advantageously, the four above identified components are present in the weight composition within the below indicated ranges:
0.1 - 2 (preferably 0.15 - 0.8) % of Sn02,
2 - 4 (preferably 2 - 3) % of Ti02,
3 - 4.5 % of Zr02, and
less than 100 ppm of Fe203.
[0024] Sn02 is efficient as fining agent. It seems also to play a role as nucleating agent and help to limit the level of titanium oxide. It is advantageously present at the indicated level of 0.1 - 2 wt. %, and it is very advantageously present at the indicated level of 15 - 0.8 wt. %. The fining efficiency and the absorption both increase with the tin oxide level.
[0025] Ti02 is advantageously present (very advantageously present) within the indicated ranges. It has to be efficient enough as nucleating agent (otherwise the material is not transparent) and not responsible of a strong absorption.
[0026] Zr02 is advantageously present within the indicated range. It has to be efficient enough as nucleating agent and not responsible of devitrification. The disclosed glasses display liquidus temperature lower than 1500°C and a viscosity at the liquidus higher than 700 dPa.s
[0027] The combination of the indicated ranges of Ti02 and Zr02 is particularly suitable. It has to be noted that the indicated preferred ranges (very advantageous variants) for Sn02 and Ti02 are independent one from the other.
[0028] Iron is an impurity which may be introduced by the raw materials. Iron can be present at a concentration of less than 100 ppm to limit absorption. Its level is advantageously less than 80 ppm, very advantageously it is less than 60 ppm.
[0029] According to a preferred variant, the glass-ceramic materials have a composition, expressed in percentage by weight of oxide, which essentially consists of:
Si02 45 - 65
A1203 14 - 28
ZnO 4 - 13
MgO 0 - 8
with ZnO + MgO ≥ 8
BaO 0 - 8
Sn02 0.1 - 2
Ti02 2 - 4
Zr02 3 - 4.5
Fe203 < 100 ppm.
[0030] It is indicated that the composition "essentially consists of the given list of compounds (oxides). This means that in the glass-ceramic materials according, the sum of the listed compounds (oxides) represents at least 95 weight %, generally at least 98 weight %. It cannot be excluded that other compounds may be found in low quantities in said glass-ceramic materials (obviously any other compounds that have not a strong detrimental action on the required properties, more particularly on transparency). So the presence of Ce02 is (quasi) excluded (the composition of the glass-ceramics generally includes no Ce02), also the significant presence of B203 (the composition of the glass-ceramics generally includes no B203). [0031] In reference to the strain point of the glass-ceramics, their composition advantageously comprise more than 55 % by weight of Si02 and within said composition, the molar ratio (R20 + R0)/A1203 is between 0.5 to 1.5, R20 being the sum of the moles of alkali oxides and RO the sum of the moles of alkaline earth oxides plus ZnO. Glass-ceramics with such composition have a high strain point, of generally at least 875°C (at least 900°C).
[0032] A1203 is one of the main component of the crystals. It can be present at a minimum amount to ensure sufficient crystallization and not at a too high amount to then produce an unacceptable devitrification of mullite, hence the above indicated preferred range.
[0033] ZnO and MgO are also constituents of the crystals. Therefore a minimum amount can be incorporated. At a too high level, MgO is detrimental for transparency. The above indicated preferred values take that into account.
[0034] BaO stays in the residual glass. It has been observed that it helps in having a good transparency but its amount has to be limited to keep enough crystallinity and a high strain point, hence the above indicated preferred range.
[0035] The man skilled in the art has now realized the great interest of the glass-ceramics disclosed herein.
[0036] The precursor glass as well as the glass-ceramics are environmentally free (are arsenic and antimony free). The precursor glass is easily formed.
[0037] The glass-ceramics are transparent and display a high transmission above 400 nm which, combined with a high strain point, more particularly makes them suitable as superstrate for photovoltaic cells.
[0038] Some of the glass-ceramics are more particularly suitable to support the high temperature growth of a mono crystalline or poly crystalline semiconductor layer. Such growth may consist in the epitaxial thickening of a seed layer formed on the glass-ceramic material. The seed layer may be a large grain polycrystalline silicon layer formed by Aluminum Induced Crystallization or Aluminum Induced Layer Exchange (O. Nast, T. Puzzer, L.M. Koschier, A.B. Sproul, S.R. Wenham, Appl. Phys. Lett. 73 (1998) 3214), or may be a monocrystalline silicon layer (WO 2008/121262). The epitaxial thickening of such layers is advantageously performed at temperatures above 800 °C, and more advantageously performed at temperatures above 1000°C (I. Gordon et al, Solar Energy Materials & Solar Cells 94 (2010) 381-385). Another means of achieving a high quality polycrystalline silicon layer is to perform a high temperature rapid thermal annealing step of a previously grown polycrystalline silicon layer (B. Rau et al, Materials Science and Engineering B 159-160 (2009) 329-332).
[0039] Photovoltaic cells usually include at least one transparent conductive layer located between the superstrate and the at least one semiconductor absorber layer. Such a transparent conductive layer allows the collection of the charge carriers generated in the semiconductor absorber layer, while allowing most of the photons to reach the semiconductor absorber layer. The transparent conductive layer may be a transparent conductive oxide layer, or more advantageously, in the case of an epitaxial thickening of a seed layer, may be the seed layer itself in the event that it is a highly doped layer. The transparent conductive layer usually has significant absorption below a wavelength of 400 nm, which does not result in the generation of collectable charge carriers. Therefore a superstrate should preferably have a high transmission for wavelengths above 400 nm. In the preferred case of an epitaxially thickened seed layer, where the seed layer also acts as the conductive layer, this semi-transparent conductive layer usually has significant absorption up to a wavelength of about 450 nm. In this case, a superstrate should preferably have a high transmission for wavelengths above 450 nm. In this way the glass-ceramics of the invention are particularly suitable as superstates for photovoltaic cells.
[0040] According to its second subject-matter, the present disclosure relates to alumino-silicate glass materials which are precursor of the glass-ceramic materials described above. Such glass materials advantageously have the compositions indicated above (for the glass-ceramics). Within said compositions, the level of zirconium oxide can be kept at a low enough level to limit devitrification. The co- presence of Ti02 and Zr02 allows the requirements to be satisfied.
[0041] The present invention also relates to articles made of glass-ceramic materials described above. Such glass-ceramic articles may present any shape and may be aimed to any use. Advantageously, they consist in a sheet. Such sheets generally have a thickness in the range of 0.5 to 4 mm. Such sheets are advantageously used as support (substrate) for semiconductor thin films.
[0042] According to a further embodiment, the present disclosure relates to a method for manufacturing an article made of a glass-ceramic material as described above. Said method successively includes melting of a batch mixture of raw materials able to vitrify, said batch mixture containing Sn02 as refining agent, followed by refining of the molten glass obtained, cooling of the refined molten glass obtained, and simultaneously forming it into a desired form for the targeted article, and ceramming of said formed glass, said batch mixture being a precursor of a glass-ceramic material as described above.
[0043] Said method is characteristically carried out with a suitable mineral batch mixture (including Sn02 as fining agent, Ti02 and Zr02 as nucleating agents and less than 100 ppm of Fe203, advantageously in the amounts as more precisely described above) and with a suitable heat-treatment which provides a spinel glass-ceramic.
[0044] The ceramming treatment generally comprises the two steps: a nucleation step (in the 700-850°C range) and a step of crystal growth (in the 850 -
1050°C range). At least one hour is required for each of these steps.
[0045] The forming step of said method is advantageously carried out to produce a sheet. Thus, it very advantageously consists in rolling (between rollers) or in a float process. The produced sheet generally has a thickness of 0.5 to 4 mm.
[0046] Any sheet produced by the above method, more generally any sheet in a glass-ceramic, is opportunely a part of a structure including, further to said sheet, at least one layer made of a semi-conductor (arranged on said sheet). Such a structure constitutes a further subject-matter.
[0047] Lastly, the disclosure relates to electronic and optoelectronic devices comprising such a structure (glass-ceramic sheet + at least one layer made of a semi-conductor). Such devices may consist in a photovoltaic device, a flat panel display device, a liquid crystal display device. Said list is in no way exhaustive.
[0048] The man skilled in the art has understood the great advantage of the spinel glass-ceramic materials. They are transparent, free of As203 and Sb203, easy to obtain and can also be able to withstand high temperature. So they are able to constitute perfect support for crystalline silicon thin films.
[0049] The present invention is now illustrated, in a non limitative way, by the following examples (1 to 6) Said examples may be compared to given comparative examples (A to D).
[0050] The present disclosure is also illustrated by the annexed Figure which shows the complete transmission curves (as a function of the wavelength) of some of these comparative examples (A and B) and examples (1 and 3).
Examples
[0051] The raw materials, in proportions (weight proportions expressed as oxides) copied out in the first part of Table 1 hereafter, have been mixed carefully for producing batches of 1 kg of precursor glass. It has to be noted that said raw materials includes impurities (as traces), more particularly traces of Fe2C"3.
[0052] The mixtures have been placed (for melting and refining) in platinum crucibles and melted 4 h at 1650°C.
[0053] After melting the glasses have been rolled to a thickness of 6 mm and annealed 1 h at 720°C.
[0054] Ceramming was then performed according to the following cycle:
heating to 800°C in 150 min;
maintaining at 800°C for 120 min;
heating to 1000°C in 40 min;
maintaining at 1000°C for 240 min.
[0055] The transmission measurements have been performed on 1 mm thick polished samples with a spectrophotometer equipped with an integrating sphere (this allows to measure the total, i.e. direct + diffuse, transmission). The lines "T 80%", "T 85%" and "T 90%" (of the second part Table 1 hereafter) give the wavelengths (in nm) at which the transmission values of 80%>, 85% and 90% are respectively reached. The lower values are better.
[0056] The liquidus temperatures have been measured on pieces of the precursor glasses with a volume around 0.5 cm3. These pieces were submitted to the following treatment: introduction in the furnace preheated at 1550°C;
maintenance at 1550°C for 30 min;
the temperature is decreased to the test temperature, at 10°C/min; maintenance at the test temperature for 17h;
air quenching of the samples.
[0057] The presence of crystals is studied by optical microscopy. In Table 1 hereafter, a temperature range (and the associated viscosity range) is given as liquidus. The maximum temperature corresponds to the minimum temperature of test at which no crystal was observed; the minimum temperature corresponds to the maximum temperature of test at which crystals were observed. The nature of crystalline phase which devitrifies at the liquidus temperature is also indicated.
[0058] Strain points were measured by beam bending viscosimetry.
[0059] The linear coefficient of thermal expansion (CTE) over the temperature range 25-300°C was measured by dilatometry.
Table 1
Figure imgf000013_0001
*RO = MgO + BaO + ZnO (mo %)
[0060] Examples A, B, C and D do not belong to the invention. They are comparative examples.
[0061] The glass of comparative example A contains AS2O3. It is a glass according to US Patent No. 5,968,857.
[0062] The glass of comparative example B has quasi the same composition as the one of the glass of comparative example A. However, its composition is free of AS2O3. As explained above, it displays a low transmission.
[0063] The glass of comparative example C does not contain arsenic but a lower titanium level than the glass of comparative example B. Its transmission is higher but still low.
[0064] The glass of comparative example D contains a lower level of iron than the one of comparative example C. It displays a higher transmission but still much lower than the one of comparative example A (with AS2O3).
[0065] Examples 1-6 are inventive. Example 1 is preferred.
[0066] The annexed Figure clearly evidences that the transmission of example B is low and that transmission of examples A, 1 and 3 is higher than 80% for any wavelength above 450nm and higher than 85% for any wavelength higher than 520 nm. It also shows that the transmission of example 1 is especially interesting with a transmission higher than 80% for any wavelength higher than 400 nm.

Claims

What is claimed is:
1. A transparent glass-ceramic material containing a spinel solid solution as the main crystalline phase, having a composition that is
free of AS2O3 and Sb203, with the exception of unavoidable trace thereof, and
comprises Sn02, Ti02 and Zr02, and less than 100 ppm of Fe203.
2. The glass-ceramic material according to claim 1, wherein the composition, expressed in percentages by weight of oxides, comprises:
0.1 - 2 % of Sn02,
2 - 4 % ofTi02,
3 - 4.5 % of Zr02, and
less than 100 ppm of Fe2C"3.
3. The glass-ceramic material according to claim 1, wherein the composition, expressed in percentages by weight of oxides, essentially consists of:
Si02 45 - 65
A1203 14 - 28
ZnO 4 - 13
MgO 0 - 8
with ZnO + MgO≥ 8
BaO 0 - 8
Sn02 0.1 - 2
Ti02 2 - 4
Zr02 3 - 4.5
Fe203 < 100 ppm.
4. The glass-ceramic material according to claim 3, characterized in that its composition comprises more than 55 % by weight of Si02 and in that, within said composition, the molar ratio (R20 + R0)/A1203 is between 0.5 to 1.5, R20 being the sum of the moles of alkali oxides, and RO the sum of the moles of alkaline earth oxides plus ZnO.
5. The glass-ceramic material according to claim 1, wherein the composition, expressed in percentages by weight of oxides, comprises 0.15 to 0.8 wt. % of Sn02 and/or 2 to 3 wt. % of Ti02.
6. The glass-ceramic material according to claim 1, wherein the composition comprises less than 80 ppm of Fe203.
7. An alumino-silicate glass material, which is a precursor of a glass-ceramic material according to claim 1, the composition of which corresponds to that of a glass-ceramic material according to claim 2.
8. A glass-ceramic article made of a glass-ceramic material according to claim 1.
9. The article according to claim 8 wherein the article comprises a glass- ceramic sheet.
10. A method for manufacturing a glass-ceramic article according to claim 8, said method comprising
melting a batch mixture of raw materials able to vitrify to form a molten glass, said batch mixture containing Sn02 as refining agent,
refining the molten glass to form a refined molten glass,
cooling the refined molten glass and simultaneously forming it into a desired form, and
ceramming the form, wherein the batch mixture comprises a glass-ceramic material according to claim 1.
11. The method according to claim 10, wherein the forming comprises rolling or a float process to produce a sheet.
12. A structure comprising a sheet made of a glass-ceramic according to claim 9, said structure further comprising at least one layer made of a semiconductor formed on said sheet.
13. An electronic or optoelectronic device comprising a structure according to claim 12.
14. The device according to claim 13 comprising a photovoltaic device, a flat panel display device or a liquid crystal display device.
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